ISSN 1023-1935, Russian Journal of Electrochemistry, 2006, Vol. 42, No. 5, pp. 560565.

MAIK Nauka /Interperiodica (Russia), 2006.

Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 627632.

Corrosion Monitoring Using Electrochemical Noise

and Linear Polarization Resistance
in Fuel Oil Combustion Gas Environment*
V. M. Salinas-Bravo,a,z J. Porcayo-Calderona, and J. G. Gonzalez-Rodriguezb
a

Instituto de Investigaciones Electricas, av. Reforma 113 Col Palmira, Cuernavaca, Morelos 62490, Mexico
b CIICAp, UAEM, av. Universidad S/N, Cuernavaca, Morelos 62210, Mexico
Received July 4, 2005

AbstractCorrosion monitoring of different steels is carried out online in a combustion rig firing 32 kg/h of
fuel oil. Two temperature-controlled probes are designed to allow control of the specimens temperature and the
use of electrochemical noise (EN) and linear polarization resistance (LPR) techniques for corrosion monitoring.
Two probes are placed where the combustion gas reached a temperature of 850900, and another one at the
combustion gas exit where the rig was at 200240. Corrosion rates of an austenitic and a ferritic steel are
obtained where the temperature of the combustion gas is 850900, firing fuel oils with different content of
NaVS. Corrosion monitoring of mild steel is carried out in the test burning a fuel oil with the higher content
of NaVS by placing a corrosion probe in the low combustion gas temperature zone. The EN results show that
this technique is able to assess the corrosion rate in an environment at high temperature where fuel oil ashes
deposited and at a temperature high enough where they start to melt and a corrosion process proceeds. Results
show that this technique is able to assess the corrosivity of fuel oil ashes originated from fuel oil containing
different amounts of sodium, vanadium, and sulfur as corrosion causing impurities. Results of the low-temperature probe show that EN and LPR are able to detect the onset of corrosion on mild steel as a result of sulfuric
acid condensation on the probe. However, the corrosion rates are not the same, because localized corrosion is
taking place as detected by the EN technique. It is demonstrated that the use of two techniques for corrosion
monitoring can give a better understanding of the corrosion process. Electrochemical techniques used to assess
the corrosion resistance of alloys at high and low temperatures prove to be a valuable tool for the purposes of
materials selection or controlling the main process variables that affect the corrosion resistance of materials in
industrial equipment.
DOI: 10.1134/S1023193506050156
Key words: online corrosion monitoring, electrochemical noise, linear polarization, high-temperature corrosion, fuel oil ashes

INTRODUCTION
Corrosion monitoring for industrial and process
applications is a key issue to achieve high standards of
reliable and safe operation. Different techniques for
monitoring corrosion rate have been developed [1, 2].
However, the choice of the right technique and the
appropriate corrosion probe design is very important
for a successful online corrosion monitoring program.
Linear polarization resistance (LPR) is one of the
first techniques used for corrosion monitoring. This
technique is well known and documented [3, 4]. Lately,
the electrochemical noise technique (EN) has been
incorporated for corrosion monitoring in different
industries.
In the power industry, EN has been applied to monitor corrosion of materials performing in a high-tem* The text was submitted by the authors in English.
z Corresponding author, email: vsalinas@iie.org.mx

perature gas environment with the presence of molten

salts characteristic of coal-fired boilers for monitoring
furnace wall corrosion [57] and superheater corrosion
[8].
Molten deposits formed on furnace wall tubes of
coal-fired boilers consist of a mixture of alkali-metal
sulfate mixed with iron sulfide and pyrosulfates [9].
However, in superheater tubes, composition of deposits
formed are mainly alkali iron trisulfates [10].
Composition of molten deposits formed in fuel oil
boilers is different from those formed in coal-fired boilers because of the nature of the fuel.
Residual fuel oil contains sodium, vanadium, and
sulfur impurities, forming compounds like Na2SO4,
V2O5, and complex vanadates by reaction in the combustion system [11]. Complex molten vanadates are relatively low melting-point compounds acting as a flux

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CORROSION MONITORING USING ELECTROCHEMICAL NOISE

removing protective oxide scales from superheater

tubes, producing accelerated corrosion rates [12].
Corrosion monitoring using EN and electrochemical impedance (EI) in gas environments where dew
point corrosion may be the case has been done under
condenser nitric acid conditions [13] and in dual alkali
flue gas desulfurization system [14].
Online corrosion rate measurements using electrochemical noise have not been reported in environments
of molten ashes resulting from burning fuel oil.
The objective of this work is to investigate the
response of the EN technique to assess the corrosion
rate of boiler tube materials exposed to combustion gas
at high temperature firing two fuel oils with different
content of sodium, vanadium, and sulfur, and determine
the corrosion rate of mild steel by applying EN and
LPR techniques simultaneously in the low-temperature
flue gas.
EXPERIMENTAL
Specially designed corrosion probes were used for
corrosion monitoring. Figure 1 shows a schematic
drawing of the probes used. The main body of the probe
consists of a 63.5 mm outside diameter stainless steel
tube attached to a flange. Seven electrodes separated by
a high-temperature resistant insulation material are
positioned at the end of the tube. The thickness of electrodes is 5.0 mm and they were fabricated from ASTM
SA 213 T 22, ASTM SA 213 304, and carbon steel tube
materials. A type K thermocouple was spot-welded to
electrodes 1 and 7 on the inner diameter surface. An
NiCr wire was spot welded to the rest of electrodes in
order to allow electrical contact with the electrochemical hardware. The NiCr wires were isolated by a
ceramic fiber sleeving to avoid electric contact with the
probe body. The temperature of the electrodes in each
probe was controlled by means of a PID temperature
controller. Cooling media was provided by an instrumented system that supplied filtered and dehumidified
air. Air flow to each probe was controlled automatically
by the set point in the temperature controller.
Electrochemical hardware used for corrosion monitoring was an industrial type equipment. It has several
modules for acquiring, applying, transmitting, and processing electrical signals derived from the electrochemical noise and linear polarization techniques. Acquiring, processing, and displaying data was done with a
workstation computer. Instantaneous and time-averaged corrosion rates were calculated and recorded
along with various other statistically relevant parameters for each probe such as noise resistance, standard
deviation of current and voltage, localization index,
polarization resistance, solution resistance, etc. The
system is capable to monitor simultaneously four
probes. Electrochemical potential and current noise
were collected once per second in 300 s blocks. 5-min
average corrosion rate data were calculated and saved
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Electrode Insulator
Air inlet
Air outlet

1 2 3 4 5 6 7

Fig. 1. Schematic drawing of corrosion probes used for corrosion monitoring.

using both ECN and LPR data, along with other relevant parameters of each technique. Probe temperature
data as well was collected once per second in 300 s
blocks and recorded every 5 min as an average.
The experimental work was carried out in a combustion rig burning 32 kg/h of residual fuel oil. The design
of the combustion rig allows a combustion gas temperature gradient from exiting the furnace (1100) to the
stack (240). The high-temperature corrosion monitoring probes were inserted in the combustion gas duct
where the gas temperature was in the range 850900.
The low-temperature corrosion monitoring probe was
located in the stack duct where the combustion gas
were at 240.
Two online corrosion rate monitoring experiments
were carried out. In the first experiment, a lower content of V, Na, and S fuel oil (designated as fuel oil A)
was burned in the combustion rig, and, in the second
experiment, a higher content of V, Na, and S fuel oil
(designated as fuel oil B) was burned. Combustion conditions in both cases were the same (1% excess oxygen
in flue gas). The table shows the composition of V, Na,
and S in both fuels.
Two high-temperature probes were used in each
experiment. One probe was fitted with electrodes made
of a ferritic steel (ASTM SA 213 T 22), and the other,
with an austenitic steel (ASTM SA 213 304). In the
experiment with fuel oil B, a low-temperature corrosion
monitoring probe was positioned in the stack of the
combustion rig and was fitted with mild steel electrodes. Every test lasted 500 h. Initially, the temperature
of the two high-temperature corrosion probes was set to
Composition of impurities in fuels
Vanadium,
ppm

Sodium,
ppm

Sulfur,
wt %

Fuel oil A

226

29

3.4

Fuel oil B

280

59

3.8

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SALINAS-BRAVO et al.

600

500
1

2
0

400

10

15

20

600

500
1

2
0

300
25

700

400

Fig. 2. Corrosion rate monitoring of the probe made of ferritic steel burning fuel oil type A.

600

500

400
1
5

10

15

20

300
25

Time, h

Corrosion rate, mm/year

20

300
25

Fig. 3. Corrosion rate monitoring of probe made of ferritic

steel burning fuel oil type B.

700
Temperature, C

Corrosion rate, mm/year

15

Time, h

Time, h

10

700
2

600

500
1

2
0

Temperature, C

8
Corrosion rate, mm/year

700
Temperature, C

Corrosion rate, mm/year

Temperature, C

562

400

10

15

20

300
25

Time, h

Fig. 4. Corrosion rate monitoring of the probe made of austenitic steel burning fuel oil type A.

Fig. 5. Corrosion rate monitoring of the probe made of austenitic steel burning fuel oil type B.

400 for a period of 250 h. This allowed deposition of

fuel oil ashes on the probe surface. Afterwards, probe
temperature in each test was increased by 20 steps
every hour up to 590. This temperature was fixed and
controlled (3) for the rest of the test.
Probe temperature in the low-temperature corrosion
monitoring experiment was set at a temperature of
148. This temperature was above the dew point temperature of flue gas (140). After getting a base line
with probe temperature of 148, the probe temperature was set to 110115. Experimental conditions
like fuel oil burning rate, probe temperature, and excess
of oxygen in flue gas were kept constant through the
tests.

4 and 5 show the corrosion rate obtained in the hightemperature probes fitted with electrodes made of
ASTM SA 213 304 type austenitic stainless steel burning fuel oil A and B in the combustion rig. From
Figs. 25, it can be seen that both ferritic and austenitic
stainless steels corrode at a faster rate in the experiment
where the fuel oil with the highest content in Na, V, S
was burnt in the combustion rig.
Figure 6 shows the corrosion rate monitoring using
both electrochemical techniques (EN, LPR) simultaneously in the low-temperature probe fitted with mild
steel electrodes. This experiment was carried out burning fuel oil type B in the combustion rig.
The sensitivity of the EN technique to a change in
the electrode temperature was investigated in the test
burning fuel oil type B. Figure 7 shows that a change in
the probe temperature resulted in a change in corrosion
rate. In this case, the corrosion rate reached a maximum
value, then decreased down to a fairly constant value.
This value will correspond to the corrosion rate for the
temperature set in the probe.

RESULTS
Figures 2 and 3 show the corrosion rates obtained in
the high-temperature probes fitted with electrodes
made of ASTM SA 213 T 22 type ferritic stainless steel
burning fuel oil A and B in the combustion rig. Figures

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0.8

140

0.6

130
2

0.4

0.2
0

10

20

30

110

700

600
2
500

4
2
0

40

10

Time, h

1.2

130
0.4
2

120
110

Corrosion rate, mm/year

140

Temperature, C

Localization index

0.8

30

0.8

120
B

0.6

80

0.4

40
0.2
0

20

20

Fig. 7. Effect of increasing temperature in the electrodes

made of ASTM SA 213 304 type stainless steel, burning
fuel oil type B in the combustion rig.

150

1.2

10

15

Time, h

Fig. 6. Corrosion monitoring in the low-temperature probe

made of mild steel.

400

Temperature, C

120

563

Temperature, C

150
Corrosion rate, mm/year

1.0

Temperature, C

Corrosion rate, mm/year

CORROSION MONITORING USING ELECTROCHEMICAL NOISE

40

20

40

0
60

Time, h

Time, h

Fig. 8. Change in the localization index monitoring using

EN data in the low-temperature probe as a function of time.

Fig. 9. Corrosion rate response of the low-temperature

probe in terms of the oxygen percentage in the flue gas.

Results of the low-temperature probe showed that,

while the probe temperature is kept above the acid dew
point temperature of the flue gas (140), the response
of both techniques is minimal. As soon as the temperature of the electrodes is set to a temperature below the
acid dew point temperature of flue gas, the response of
both techniques starts to show.

DISCUSSION

Localization index monitoring was obtained from

the EN data in the low-temperature probe (see Fig. 8).
The response to a change in combustion conditions
(% 2 in flue gas) was also investigated. Figure 9
shows the response of the probe in terms of the change
of the corrosion rate with the oxygen content in the flue
gas, when the probe temperature was set just below the
acid dew point temperature. It can be seen that an
increase in the oxygen contents increases the corrosion
rate about 0.2 mm/year when the percentage in oxygen
increases by 1%.
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The results obtained using EN for corrosion monitoring in a high-temperature gas environment where
flue oil ashes are deposited have demonstrated that this
technique can be used in this environment. This technique was able to assess the corrosion rate of materials
exposed to fuel oil ashes derived from fuel oil having
different amounts of Na, V. Fuel oil ash corrosivity has
been documented taking into account the content of Na,
V, S in ashes [13, 14] or Na, V in the fuel oil [1719].
In this case, higher corrosion rates were obtained for
both steels tested with fuel oil B, which is the fuel oil
with higher amounts of Na, V and sulfur. The EN sensitivity to a change in the electrode temperature was
confirmed. The response of the technique to a change in
probe temperature was very good as can be observed in
Fig. 7. This is important for assessing the corrosion rate
of materials at different temperatures in a corrosive
environment.
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SALINAS-BRAVO et al.

An important issue that has to be taken into account

for corrosion monitoring using high-temperature
probes in flue gas is the probe conditioning. Before corrosion monitoring starts, it is necessary to allow deposition of fuel oil ashes on the probe electrodes. This is
achieved by setting the probe temperature between
100150 lower than the temperature where corrosion is expected to start. Another important aspect to
bear in mind for corrosion monitoring in high-temperature gas environments is the fact that two processes are
taking place at the same time on the probe: the deposition of fuel oil ashes and the consumption of corrosive
species deposited because of the corrosion process.
Figure 7 shows how an increase in probe temperature
results in an increase in corrosion rate up to a maximum
value, then decreases and reaches a steady value. This
suggests that, after increasing the probe temperature,
there are enough corrosive species deposited and this
allows higher corrosion rates. As the corrosion process
continues, aggressive species are consumed and corrosion rate values start to decrease until a constant value
is obtained. A constant value is obtained when equilibrium exists between ash deposition rate and corrosion
rate.
Corrosion monitoring in the low-temperature probe
using both EN and LPR techniques provided interesting
results. After the probe temperature was set to 115,
this is below the acid dew point temperature of flue gas
(140), corrosion rate obtained by LPR technique
started to increase, and EN corrosion rate values seem
to change little with respect to the base line obtained
with the probe temperature of 148 (Fig. 7). The difference in corrosion rates between the two techniques
can be explained because of the type of corrosion that
is taking place on the probe electrodes.
Localization index monitoring recorded at the same
time that EN data was taken is shown in Fig. 8. From
this figure, it can be observed that, after the probe temperature has set to 115, some localization index
events start to appear for a period of approximately
12 h. After this time, localization index values start to
increase reaching values near 1.0. This is an indication
that localized corrosion is taking place on the electrodes. Therefore, corrosion rates obtained with EN
technique in this particular environment have to be analyzed carefully. The advantage of using two electrochemical techniques simultaneously allows to investigate the kind of corrosion process that is taking place.
In corrosion monitoring, it is important that a
change in a process variable that affects corrosion rate
of materials can be detected by the corrosion probe
employed. A change in the O2 percentage in flue gas
was made while corrosion monitoring was taking place
(Fig. 9). An increase in the oxygen percentage in flue
gas from 1 to 2% resulted in an increase in corrosion
rate while keeping probe temperature constant. After

changing oxygen concentration in flue gas back to 1%,

the corrosion rate of the mild steel electrodes went back
to values close to those obtained before the increase. A
higher oxygen concentration in flue gas increases the
amount of SO3 and water vapor; therefore, the amount
of sulfuric acid condensing is higher. This explain a
higher corrosion rate in these conditions. Decreasing
oxygen concentration in flue gas brings the opposite.
Proper design of a corrosion probe in corrosion
monitoring is a key issue for a successful monitoring
program. In this case, the probe design employed for
high- and low-temperature corrosion monitoring in flue
gas from burning fuel oil gave good results in terms of
corrosion rate and response to process variables.
CONCLUSIONS
Electrochemical noise technique was successfully
applied to online monitor corrosion rate in a flue gas
environment resulting from burning fuel oil. This technique was able to detect the change in corrosion rate of
materials exposed to high-temperature flue gas derived
from two fuel oils having different contents of NaV
S. Probe conditioning is an important issue to be taken
into account in high-temperature corrosion monitoring.
Otherwise results may be uncertain. Low-temperature
corrosion monitoring in flue gas environment using EN
and LPR techniques simultaneously prove to be a valuable approach in order to understand the corrosion process that is taking place in such environment. Finally,
probe design and probe response to a change in a process condition it is very important to carry on a successful corrosion rate monitoring program in industry.
REFERENCES
1. Jaske, C.E., Beavers, J.A., and Thompson, N.G., Corrosion Prevention and Control, 2002, vol. 49, p. 3.
2. Kane, R.D. and Cayard, M.S., Chem. Eng. Prog., 1999,
vol. 94, no. 10, p. 49.
3. Industrial Corrosion Monitoring, London: HMSO,
1978.
4. Callow, L.M., Richardson, J.A., and Dawson, J.L., Br.
Corros. J., 1976, vol. 11, p. 123.
5. Farrell, D.M., Mok, W.Y., and Finder, L.W., Mater. Sci.
Eng., 1989.
6. Linjewile, T.M., Valentine, J., Davis, K.A., Harding, N.S., and Cox, W.M., Mater. High Temp., 2003,
vol. 20, p. 175.
7. Davis, K., Lee, C., Seeley, R., Harding, S., Heap, M., and
Cox, W., Proc, 25th Int. Conf. on Coal Utilization and
Fuel Systems, March, 2000, Florida, p. 25.
8. Whitlow, G.A., Mok, W.Y., Sox, W.M., Gallager, R.J.,
Lee, S.Y., and Elliot, R., Corrosion-1991, Cincinati
(OH), NACE International, paper 254.

RUSSIAN JOURNAL OF ELECTROCHEMISTRY

Vol. 42

No. 5

2006

CORROSION MONITORING USING ELECTROCHEMICAL NOISE

9. Harb, J.N. and Smith, E.E., Prog. Energy Combust. Sci.,
1990, vol. 16, p. 169.
10. Scrivastava, S.C., Godiwalla, K.M., and Baner Jee, M.K.,
J. Mater. Sci., 1997, vol. 32, p. 835.
11. Gitanjaly, PrakashS. and Singh, S., Br. Corros. J., 2002,
vol. 37, p. 56.
12. Paul, L.D. and Seeley, R.R., Corrosion-1990, Las Vegas
(NV), NACE International, paper 267.
13. Harada, Y., Matsuo, T., and Naito, S., Proc. of 2nd Int.
Conf on Future of Heavy Crude and Tar Sands, 1984
p. 2.

RUSSIAN JOURNAL OF ELECTROCHEMISTRY

Vol. 42

565

14. Kawamura, T. and Harada, Y., Mitsubishi Tech. Bull.,

1980, no. 139.
15. Hladky, K., John, D.G., Whorthington, S.E., and Herbert, D., UK Corrosion-1985, Harrogate (UK).
16. Farrel, D.M., Cox, W.M., Wrobel, B.A., and Syret, B.C.,
Solving Corrosion Problems in the Air Pollution Control
Industry, Buffalo (NY), 1987.
17. Demo, J.J., Corrosion-1978, Houston (TX), NACE International, paper 98.
18. Elliot, P., et al., J. Inst. Fuel, 1973, vol. 46, no. 385,
p. 35.
19. Coats, A.W., J. Inst. Fuel, 1969, vol. 42, no. 337, p. 75.

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